CN109806842A - A kind of thioether functionalization covalent organic frame material and its preparation method and application with triazine structure - Google Patents
A kind of thioether functionalization covalent organic frame material and its preparation method and application with triazine structure Download PDFInfo
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- CN109806842A CN109806842A CN201910210421.XA CN201910210421A CN109806842A CN 109806842 A CN109806842 A CN 109806842A CN 201910210421 A CN201910210421 A CN 201910210421A CN 109806842 A CN109806842 A CN 109806842A
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Abstract
The present invention discloses a kind of thioether functionalization covalent organic frame material and its preparation method and application with triazine structure, belongs to technical field of material.Contain acylhydrazone key, triazine group and ethyl thioether group in the covalent organic frame material structure simultaneously, since nitrogen in structure and sulphur atom component are abundant, the photocatalytic activity of covalent organic frame material is enhanced to a certain extent, producing on hydrogen field based on the covalent organic frame material of triazine structure in photocatalysis Decomposition seawater for thioether functionalization is set to have good application prospect, and its preparation condition is mild, it is easy to operate, clean energy, it is environmentally protective, it is low in cost, there is biggish application potential.
Description
Technical field
The invention belongs to technical field of material, and in particular to a kind of thioether functionalization with triazine structure covalently has
Machine frame frame material and its preparation method and application.
Background technique
About 97% water is seawater (3.0 ~ 5.0% salt) on the earth, this shows if sea brine can be directly used as the energy,
Seawater will provide unlimited water supply.Photocatalysis Decomposition seawater is a particularly important technological progress process, be can use abundant
Solar energy be directly realized by proton reduction, obtaining clean Hydrogen Energy helps to alleviate or even solves current environmental problem and the energy
Problem.
Therefore the photocatalysis hydrogen production technology to be grown up based on hydrogen energy source is gradually by the concern of researchers and attention.
Traditional catalyzing manufacturing of hydrogen materials most concentrates on inorganic semiconductor material, the rare report of poromerics of some lightweight element compositions
Road, and the covalent organic frame material of the triazine structure rich in N component has preferable photocatalytic hydrogen production activity, can especially lead to
Cross the methods of metal-doped its photocatalytic hydrogen production activity of raising.
Summary of the invention
The thioether functionalization with triazine structure that it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of is total
Valence organic framework materials and the preparation method and application thereof.And there can be preferable application on photocatalysis Decomposition seawater production hydrogen.
For achieving the above object, the present invention adopts the following technical scheme:
A kind of thioether functionalization covalent organic frame material (TTR-COF) with triazine structure, structural unit are as follows:
, connect on phenyl ring "" indicate the repetitive structure list omitted
Member.
A kind of thioether functionalization covalent organic frame material with triazine structure the preparation method comprises the following steps: by the bis- (2- of 2,5-
(ethylmercapto group) ethyoxyl) terephthalhydrazide and 4,4', 4''- (three base of 1,3,5- triazine -2,4,6-) three [benzaldehydes] are added to
It in Isosorbide-5-Nitrae-dioxane/mesitylene/acetic acid mixed system reaction tube, is reacted 3 ~ 5 days in 100 ~ 120 DEG C, being made has triazine
The thioether functionalization covalent organic frame material TTR-COF of structure.
A kind of preparation method of the thioether functionalization covalent organic frame material with triazine structure, specifically includes following step
It is rapid:
(1) by bis- (2- (ethylmercapto group) ethyoxyl) terephthalhydrazides of 2,5- and 4,4', 4''- (1,3,5- triazine -2,4,6- three
Base) three [benzaldehydes] are added in Isosorbide-5-Nitrae-dioxane/mesitylene/acetic acid mixed system reaction tube, and sonic oscillation 10 minutes；
(2) then reaction tube is rapidly frozen and is thawed in liquid nitrogen bath, vacuumized three times, until the internal pressure of 0 mbar is gone forward side by side
The sealing of row flame；
(3) after being warming up to room temperature, reaction tube is placed in 100 ~ 120 DEG C and reacts 3 ~ 5 days, generates yellow solid precipitate；
(4) collected by suction sediment is washed three times with anhydrous tetrahydro furan, then three times with acetone washing, by yellow powder 80
It DEG C is dried in vacuum overnight, the thioether functionalization covalent organic frame material TTR-COF with triazine structure is made.
In above-mentioned preparation method, bis- (2- (ethylmercapto group) ethyoxyl) terephthalhydrazides and 4,4' of 2,5- in step (1),
The molar ratio of 4''- (three base of 1,3,5- triazine -2,4,6-) three [benzaldehydes] is 3:2.
In above-mentioned preparation method, in step (1) 4,4', 4''- (1,3,5-triazines -2,4, tri- base of 6-) three [benzaldehydes] with
The molar ratio of acetic acid is 1:(8 ~ 12).
In above-mentioned preparation method, the volume ratio of Isosorbide-5-Nitrae-dioxane, mesitylene and acetic acid is 5:15:4 in step (1).
A kind of thioether functionalization covalent organic frame material with triazine structure has good response to visible light, answers
In terms of producing hydrogen for photocatalysis Decomposition seawater.
A kind of thioether functionalization covalent organic frame material with triazine structure is in terms of photocatalysis Decomposition seawater produces hydrogen
Application, sacrifice donor be triethanolamine (TEOA), co-catalyst be noble metal Au ion.
The beneficial effects of the present invention are:
1) by the present invention in that with bis- (2- (ethylmercapto group) ethyoxyl) terephthalhydrazides of 2,5- and 1,3,5- tri--(4- formoxyl-
Phenyl) triazine be reaction raw materials, under Isosorbide-5-Nitrae-dioxane/mesitylene/aqueous acetic acid mixed system solvent thermal reaction close
At a kind of thioether functionalization covalent organic frame material with triazine structure is obtained, synthetic yield is relatively high, to visible
Light has good response, and producing hydrogen field in photocatalysis Decomposition seawater has good potential using value.
2) equipment and chemical reagent used in synthetic method of the present invention are easily obtained, and technological operation is easy, strong applicability,
Industrial application value is high, utilization easy to spread.
Detailed description of the invention
Fig. 1 is the X-ray powder diffraction figure of 1 gained TTR-COF of embodiment；
Fig. 2 is the nuclear magnetic resonance of 1 gained TTR-COF of embodiment13C CP/MAS NMR spectra；
Fig. 3 is the nitrogen adsorption desorption curve figure of 1 gained TTR-COF of embodiment；
Fig. 4 is that 1 gained TTR-COF of embodiment photocatalysis circulation under the conditions of pure water produces hydrogen test chart；
Fig. 5 is that 1 gained TTR-COF of embodiment photocatalysis circulation under the conditions of simulated seawater produces hydrogen test chart.
Specific embodiment
It is easy to understand in order to which the purpose of the present invention, technical solution and advantage is more clearly understood, with reference to embodiments,
The present invention will be described in further detail.It is appreciated that specific embodiment described herein is used only for explaining the present invention,
It is not intended to limit the present invention.In addition, technical characteristic involved in the various embodiments of the present invention described below is only
Not constituting a conflict with each other can combine.
Embodiment 1
A kind of preparation method of the thioether functionalization covalent organic frame material with triazine structure:
By bis- (2- (ethylmercapto group) ethyoxyl) terephthalhydrazides (15.4 mg, 38.13 μm of ol) of 2,5- and 4,4', 4''- (1,
Three base of 3,5- triazine -2,4,6-) three [benzaldehydes] (10.0 mg, 25.42 μm of ol) be added to 1.2 mL 1,4- dioxane/
(body long 20 cms, neck length 1 in mesitylene/acetic acid mixed system (v:v:v=5:15:4), are placed in 5 mL Pyrex pipes
Cm), it is ultrasonically treated 10 minutes.Then Pyrex pipe is rapidly frozen and is thawed in liquid nitrogen bath, vacuumized three times, until 0 mbar
Internal pressure and carry out flame sealing.After being warming up to room temperature, Pyrex pipe is placed in 120 DEG C of baking oven and is reacted 3 days, generated
Yellow solid.Collected by suction sediment, is washed three times with anhydrous tetrahydro furan, then three times with acetone washing.Yellow powder is existed
80 DEG C are dried in vacuum overnight, and obtain the thioether functionalization covalent organic frame material TTR-COF with triazine structure.
The X-ray of thioether functionalization covalent organic frame material TTR-COF manufactured in the present embodiment with triazine structure
Powder diagram is shown in Fig. 1, nuclear magnetic resonance13C CP/MAS NMR spectra is shown in that Fig. 2, nitrogen adsorption desorption curve figure are shown in Fig. 3.TTR-
The crystallinity of COF determines that PXRD figure shows TTR-COF in 2 θ=2.4 by powder x-ray diffraction (PXRD) analysiso, 4.7o,
6.0 oWith 26.3oLocate appearance, respectively corresponds 100,110,200 and 001 crystal faces (Fig. 1).The solid-state 13C NMR light of TTR-COF
Spectrum shows the resonance signal of 160 ppm, corresponds to the carbon atom in TTR-COF structure in hydrazone bond, in addition the peak at 169 ppm
Value is attributed to the carbon atom in triazine ring, and the signal at 14 and 31 ppm confirms that there are sulfide group (Fig. 2) in frame.Pass through
N2Adsorption/desorption is tested to study the porosity of TTR-COF, and the specific surface and pore volume of TTR-COF is respectively 138 m2 g-1With
0.09 cm3 g-1(Fig. 3).
2 TTR-COF of embodiment photocatalysis circulation under the conditions of pure water produces hydrogen test
TTR-COF prepared by 20 mg embodiments 1 is suspended in as photochemical catalyst containing 10% triethanolamine/pure water (V/V)
50 mL solution in, be added dropwise 1.0 wt% Au as co-catalyst, disperse 5 minutes in ultra sonic bath, in visible light (>=420
Nm it under irradiation), carries out photocatalysis Decomposition pure water and produces hydrogen, circulation experiment carries out 5 times, every time 4 hours.TTR-COF is in pure water item
Photocatalysis circulation production hydrogen test chart is shown in Fig. 4 under part.Known by Fig. 4, the hydrogen manufacturing total amount of TTR-COF is in first time operation to 4 hours tables
It is now 1720 μm of ol g-1, and carrying out circulation experiment at radiation of visible light (nm of λ >=420) can be small with steady testing 20
When.
3 TTR-COF of embodiment photocatalysis circulation under the conditions of simulated seawater produces hydrogen test
TTR-COF prepared by 20 mg embodiments 1 is suspended in as photochemical catalyst containing 10% triethanolamine/seawater (V/V)
50 mL solution in, be added dropwise 1.0 wt% Au as co-catalyst, disperse 5 minutes in ultra sonic bath, in visible light (>=420
Nm it under irradiation), carries out photocatalysis Decomposition seawater and produces hydrogen, circulation experiment carries out 5 times, every time 4 hours.TTR-COF is in simulation sea
Photocatalysis circulation production hydrogen test chart is shown in Fig. 5 under the conditions of water.Known by Fig. 5, at radiation of visible light (nm of λ >=420), TTR-COF
The average liberation of hydrogen total amount of each photocatalysis circulation can reach 500 μm of ol g-1。
It is discussed in detail although the contents of the present invention have passed through above preferred embodiment, but it should be appreciated that above-mentioned
Description should not be considered as limitative to the invention.After those skilled in the art have read above content, for the present invention
A variety of modifications and substitutions will be apparent from.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (8)
1. a kind of thioether functionalization covalent organic frame material with triazine structure, which is characterized in that its structural unit are as follows:
, connect on phenyl ring "" indicate the repetitive structure list omitted
Member.
2. a kind of preparation side of the thioether functionalization covalent organic frame material with triazine structure as described in claim 1
Method, it is characterised in that: by bis- (2- (ethylmercapto group) ethyoxyl) terephthalhydrazides and 4,4' of 2,5-, 4''- (1,3,5-triazines -2,
4,6- tri- bases) three [benzaldehydes] are added in Isosorbide-5-Nitrae-dioxane/mesitylene/acetic acid mixed system, and it is anti-in 100 ~ 120 DEG C
It answers 3 ~ 5 days and the thioether functionalization covalent organic frame material with triazine structure is made.
3. the preparation method of the thioether functionalization covalent organic frame material according to claim 2 with triazine structure,
It is characterized in that, specifically includes the following steps:
(1) by bis- (2- (ethylmercapto group) ethyoxyl) terephthalhydrazides of 2,5- and 4,4', 4''- (1,3,5- triazine -2,4,6- three
Base) three [benzaldehydes] are added in Isosorbide-5-Nitrae-dioxane/mesitylene/acetic acid mixed system reaction tube, and sonic oscillation 10 minutes；
(2) then reaction tube is rapidly frozen and is thawed in liquid nitrogen bath, vacuumized three times, until the internal pressure of 0 mbar is gone forward side by side
The sealing of row flame；
(3) after being warming up to room temperature, reaction tube is placed in 100 ~ 120 DEG C and reacts 3 ~ 5 days, generates yellow solid precipitate；
(4) collected by suction sediment is washed three times with anhydrous tetrahydro furan, then three times with acetone washing, by yellow powder 80
It DEG C is dried in vacuum overnight, the thioether functionalization covalent organic frame material with triazine structure is made.
4. the preparation method of the thioether functionalization covalent organic frame material according to claim 3 with triazine structure,
It is characterized by: bis- (2- (ethylmercapto group) ethyoxyl) terephthalhydrazides of 2,5- and 4,4', 4''- (1,3,5- tri- in step (1)
Three base of piperazine -2,4,6-) three [benzaldehydes] molar ratio be 3:2.
5. the preparation method of the thioether functionalization covalent organic frame material according to claim 3 with triazine structure,
It is characterized by: the molar ratio of 4,4' in step (1), 4''- (three base of 1,3,5- triazine -2,4,6-) three [benzaldehydes] and acetic acid
For 1:(8 ~ 12).
6. the preparation method of the thioether functionalization covalent organic frame material according to claim 3 with triazine structure,
It is characterized by: the volume ratio of 1,4- dioxane, mesitylene and acetic acid is 5:15:4 in step (1).
7. a kind of thioether functionalization covalent organic frame material with triazine structure as described in claim 1 is in photocatalysis point
Solve the application in terms of seawater produces hydrogen.
8. the thioether functionalization covalent organic frame material according to claim 7 with triazine structure is in photocatalysis Decomposition
Seawater produces the application in terms of hydrogen, it is characterised in that: sacrifice donor used is triethanolamine (TEOA), and co-catalyst is noble metal Au
Ion.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110075919A (en) * | 2019-06-04 | 2019-08-02 | 中国科学院上海高等研究院 | Containing column [5] aromatic hydrocarbons conjugated polymer as the purposes of catalyst in photochemical catalytic oxidation thioether |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694469A (en) * | 2013-12-17 | 2014-04-02 | 兰州大学 | Sulfide functionalized covalent organic frame material and synthesis method thereof |
| CN107129583A (en) * | 2017-05-25 | 2017-09-05 | 西北师范大学 | The synthetic method of porous organic covalent frame material with triazine structure |
| CN108889334A (en) * | 2018-06-05 | 2018-11-27 | 华中科技大学 | A kind of application containing heteroatomic triazine covalent organic frame material in photocatalysis |
| CN109174009A (en) * | 2018-08-30 | 2019-01-11 | 中山大学 | Aptamers modify the covalent organic frame composite material of triazine, preparation method and application |
-
2019
- 2019-03-20 CN CN201910210421.XA patent/CN109806842B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694469A (en) * | 2013-12-17 | 2014-04-02 | 兰州大学 | Sulfide functionalized covalent organic frame material and synthesis method thereof |
| CN107129583A (en) * | 2017-05-25 | 2017-09-05 | 西北师范大学 | The synthetic method of porous organic covalent frame material with triazine structure |
| CN108889334A (en) * | 2018-06-05 | 2018-11-27 | 华中科技大学 | A kind of application containing heteroatomic triazine covalent organic frame material in photocatalysis |
| CN109174009A (en) * | 2018-08-30 | 2019-01-11 | 中山大学 | Aptamers modify the covalent organic frame composite material of triazine, preparation method and application |
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| CN110075919B (en) * | 2019-06-04 | 2022-02-22 | 中国科学院上海高等研究院 | Application of column [5] containing arene conjugated polymer as catalyst in photocatalytic oxidation of thioether |
| CN113754884A (en) * | 2020-06-01 | 2021-12-07 | 南京工业大学 | Two-dimensional covalent organic framework material based on phenoxazine and preparation method and application thereof |
| CN112500546A (en) * | 2020-11-02 | 2021-03-16 | 西安理工大学 | Preparation method of spherical porous structure two-dimensional covalent organic framework material |
| CN112500546B (en) * | 2020-11-02 | 2022-06-07 | 西安理工大学 | Preparation method of spherical porous structure two-dimensional covalent organic framework material |
| CN112500545A (en) * | 2020-11-27 | 2021-03-16 | 西安理工大学 | Preparation method of lamellar two-dimensional porous covalent organic framework material |
| CN112500545B (en) * | 2020-11-27 | 2022-07-01 | 西安理工大学 | Preparation method of lamellar two-dimensional porous covalent organic framework material |
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